Lubricating oils



Patented Jan. 25, 1938 PATENT OFFICE nnnmoa'rnve oms BertEIdncolnandAifredHenriksemPoncay, Okla, asslgnors,

by mesne assignments,

to -The Lubrl-Zol Development Corporation, Cleveland, Ohio, a corporation of Delaware No Drawing. Application June 22, 1932,

Serial N0. 618,794

lldGiaims.

Our invention relates to lubricting oils and more particularly-to improved methods for the production of high quality lubricating oils and such products as new compositions of matter.

It is well known that mineral lubricating oils are deflcientin oiliness characteristics, which is the most important character of the lubricant when used under conditions of boundary lubrication, where the viscosity of the lubricant plays little or no part in lubrication. Boundary lubrication conditions are obtained when engines are operating at heavy load, low speeds or, if for any reason, the supply of lubricant is cut off or not suftlcient. This last .condition may exist when for mechanical reasons the lubricant pump is not functioning properly or when the lubricant feed line is clogged with foreign matter.

It has been known that hydrocarbons of the aliphatic series, such as are found in petroleum oils or distillates, and aromatic hydrocarbons having an aliphatic side chain attached to the nucleus, such as the hydrocarbons occurring in the products of the destructive distillation of coal or wood, may be oxidized under properly controlled conditions of pressure and temperature by means of oxygen, air or other oxidizing agents, with or without the use of a catalytic agent, to produce economical yields of certain oxidation products.

'These products usually contain organic acids containing the carboxyl group and the hydroxy acids, that is, acids containing both the carboxyl group and one or more hydroxyl groups, as well as esters, lactones, aldehydes, ketones, etc.

Theoxidation process is carried on by treating the hydrocarbon to be,oxidized at an elevated temperature with an oxidizing gas under'pressure. The temperatures and pressures vary depending upon the hydrocarbon being treated and upon the speed with which the reaction is to take place, and whether or not a catalyst is used to promote the reaction. It is to be remembered that these oxidation processes are known to the art and are not to be considered part of our invenion.

One object of our invention is to provide a lubricant of high oiliness character, low coefficient of friction, and one which will act as a safety factor in lubrication when abnormal 'conditions exist for one reason or another. A

Another object .of our invention is to provide a lubricant which will maintain a very low coefficient of friction when diluted with light hydrocarbons such as are obtained in an automobile crank case by incomplete combustion of the fuel.

hereinafter fully described.

A- further object of our invention'is to provide a lubricant having penetrative lubricity characteristics. It has been found that our lubricant does not drain on the rubbing surfaces when idle,

thereby providing a lubricating film on the rub- 5 bing surfaces at all times and being of great value to the life of the machine in cold weather starting when the lubricant is very viscous and sluggish.

It has been demonstrated a number of times" 10 that hydrocarbon lubricants of the very best quality are not constant in coeiiicient of friction with slightly changing loads or speeds, and in some cases the coeflicient of friction varies over rather wide limits with some lubricants when all;

for use. To prove the emciency and value of our invention, we determine the coefllcient of friction of thegoriginal hydrocarbon lubricant by testing onthe Herschel friction testing machine, which was developed by Dr. W. H. Herschel of the United States Bureau of Standards and is well 3 known to the art. The coemcient of friction of the mixture of hydrocarbon oil and oxidation product is then determined by the same machine.

We have further found that original hydrocarbon lubricants and hydrocarbon lubricants blended with products have low film strength and have a tendency to break down and allow seizure of metals at relatively low pressures. The fllm strength of a lubricant is of great importance when the lubricant is used under heavy loads and slow speeds. By halogenating the products of this invention prior to blending with hydrocarbon lubricants-the film strength is greatly improved.

In general, our invention contemplates the ad- N dition oi small quantities of oxidation products of hydrocarbons to a petroleum hydrocarbon oil to increase the lubricity of the oil. Due to the fact that the film strength of the hydrocarbon oil, with which a small percentage of hydrocarbon oxidation products is added, is low, we haiogenate v the oindation products before their addition, in

order to increase the film strength, as be More particularly, the following example of one method of carrying out our invention is given. It is to be understood, however, that this example is not to be considered a limitation of our invention, but is merely given by way of illustration to enable those skilled in the art to practice our invention.

We oxidize hydrocarbons and wax to form acids and esters by any of the methods shown in the following patents: Burwell, 1,690,769; Mackenzie et al., 1,705,298; Pungs et al., 1,787,- 951; McCoull, 1,767,147; Burwell, 1,690,768. The oxidation product thus obtained, as for example according to the Burwell process, in which a petroleum hydrocarbon oil is oxidized in the presence of a manganese compound in the neighborhood of 120 C. under about 300 pounds" pressure, is then treated with chlorine at room temperature. Excess chlorine and hydrogen chloride are removed by warming and washing with solvents. The product thus-prepared was then added to a sample of high quality lubricant and tested on the Tlmken machine, which is a machine for determining film strength of lubricants, developed and manufactured by the Timken Roller Bearing Company and well known in the art. A sample of the original hydrocarbon lubricant was also tested on the Timken machine. Likewise the hydrocarbon lubricant with the addition of the aforedescribed oxidation product was tested on the Timken machine. The

following results were obtained:

Film Pound Prodmt wci m fiaffg f inch Original hydrocarbon 18.2 10, 500 Original hydrocarbon plus 56 oi 1% of oxida+ tion prfiduchnsagufis. Lula 2o. 7 12,000

YdlOcfll' f 1 0i 6 orinated oxidation prodgctnfiun? 86. 2 33.000

It will be obvious from the foregoing that the film strength obtained by the addition of a small quantity of a chlorinated oxidation product will practically double the fllm strength.

The oxidation product appears to be a mixture of acids, hydroxy acids, esters, lactones, etc., of rather indefinite and widely varying composition. This, however, is unimportant inasmuch as it is efllcient and produces the results upon which the invention is based. Varying quantities of' chlorinated product may be added depending upon the quality of the initial lubricant. As a general rule, we have found that quantities varying from 0.1% to 2% are sufllcient for normal lubricants of salable quality. We have found that a limiting percentage is usually reached ai'ter which the film strength does increase for the particular lubricating oil with which the halogenated oxidation product is added. In some cases it may be necessary to add as much as 5%,

if the lubricant is of a very poor quality, to obtain a marked increase in the film strength.

A mineral oil which had a ooemcient of friction of .140 as tested on the Herschel machine was again tested after the addition of a small percentage of the oxidation .product of a hydrocarbon oil obtained as described above. The resulting coei'ilclent of friction was .075, clearing showing a marked increase in the lubricating quality of the oil.

is within the scope of our claims. It is further obvious that various changes may be made in details within the scope of our claims without departing from the spirit of our invention. It is. therefore, to be understood that ourinvention is not to be limited to the specific details shown and described.

Having thus described our invention, what we claim is:

1. A lubricating 011 comprising in combination,-

a major quantity of a hydrocarbon oil and a minor quantity of the halogenated oxygeniferous product obtained by chlorinating the immediate product obtained by oxidizing a lnvdrocarbon. I

2. A lubricating oil comprising in combination, a hydrocarbon oil and a small quantity of the halogenated oxygeniferous product obtained by chlorinating the immediate product obtained by subjecting a hydrocarbon to the action of oxygen under heat and pressure.

3. A lubricating oil comprising in combination a major quantity of a hydrocarbon oil and a. minor quantity of a halogenated, oxygeniierous product obtained by chlorinating the immediate product obtained by oxidizing an aliphatic hydrocarbon.

4. A lubricating 011- comprising in combination a major quantity of a hydrocarbon oil and a minor quantity of the halogenated oxygeniferous product obtained by halogenating the immediate product obtained by oxidizing a hydrocarbon.

5. A lubricating oil comprising in combination a major quantity of a hydrocarbon oil and a minor quantity of a halogenated, oxygeniferous product obtained by halogenating the immediate product obtained by oxidizing an aliphatic .hydrocarbon.

6. A lubricating oil comprising in combination a major quantity of a hydrocarbon oil and a minor quantity of the halogenated oxygeniferous products obtained by halogenating the immediate product obtained by oxidizing a complex mixture of hydrocarbons.

7. A lubricating oil comprising in combination a major quantity of a hydrocarbon oil and a minor quantity of the halogenated oxygenii'erous products obtained by halogenating the immediate, product of oxidation of a hydrocarbon wax.

8. A lubricating oil comprising in combination a major quantity of a hydrocarbon oil and from 0.1% to 5% of an oxygen and halogen bearing product of the type obtained by the oxidation of hydrocarbons and the halogenation of the hydrocarbons thus oxidized.

9. A lubricating oil'comprising in combination a major quantity of a hydrocarbon 'oil and from 0.1% to 2% of an dxygenand halogen-bearing product of the type obtained by the oxidation of hydrocarbons and the halogenation of the hydrocarbons thus oxidized.

10. A lubricating-oil comprising in combination a major quantity of a-hydrocarbon oil and from 0.1% to 5% of an oxygenand chlorine-bearing product of the type obtained by the oxidation of hydrocarbons and the chlorination of the hydrocarbons thus oxidized. 

